Alkoxyalkyl phosphonates

ABSTRACT

ORGANOPHOSPHORUS COMPOUNDS, CHARACTERIZED BY THE FOLLOWING STRUCTURAL FORMULA:   Z-P(=X)(-O-R1)-X-R2   WHEREIN Z IS A C1 TO C6 ALKYL -O-CH2 GROUP, X IS EITHER OR O S, R1 IS A C1 TO C6 ALKYL GROUP, R2 IS ONE SELECTED FROM THE GROUP CONSISTING OF C1 TO C20 ALIPHATIC, C6 TO C10 AROMATIC AND HERETOCYCLIC MOIETY CONTAINING 3 TO 8 CARBON ATOMS, HAVE BEEN SHOWN TO POSSESS INSECTICIDAL PROPERTIES.

United States Patent 3,733,379 ALKOXYALKYL PHOSPHONATES Karoly Szabo, Syracuse, N.Y., assignor to Emu Research and Engineering Company No Drawing. Filed Aug. 3, 1970, Ser. No. 60,773 Int. Cl. A01n 9/36; 0071? 9/40 US. Cl. 260950 Claims ABSTRACT OF THE DISCLOSURE Organophosphorus compounds, characterized by the following structural formula:

XR: wherein Z is a C to C alkyl-O-CH group; X is either 0 or 8; R is a C to C alkyl group; R is one selected from the group consisting of C to C aliphatic, C to C aromatic and heretocyclic moiety containing 3 to 8 carbon atoms, have been shown to possess insecticidal properties.

This invention relates to novel organophosphorus compounds.

Under the prior .art, many organophosphorus compounds are known to possess insecticidal activity.

For example, British Pat. 917,085 describes and claims a class of phosphorus compounds characterized by the following generic formula:

wherein A1k=C C alkylene; R and R can be the same or difierent and each C -C alkyl and R is one selected from the group consisting of alkyl, phenylmercapto alkyl, alkylaminoalkyl, alkyl aminocarbonyl, optionally substituted phenyl, alkylmercapto or a coumaryl radical.

The disclosure in this patent is rather broad and relates to several RsC-H -analogs of the ROCH compounds disclosed and claimed in the subject application. The subject British patent discusses very little relating to the insecticidal activity of the compounds disclosed therein and it provides toxicity data on only two compounds. The data in the British patent indicates that a high concentration of these compounds is required in order to mites and also these compounds possess a high toxicity.

Therefore, the compounds of the subject application are distinguished not only by its excellent insecticidal action, but also by its greatly reduced mammalian toxicity.

The organophosphorus compounds of the subject invention can be characterized by the following structural formula:

wherein Z is a C to C alkyl--O-CH group; X is either 0 or S; R is a C to C alkyl group; R is one selected from the group consisting of C to C aliphatic, C to C aromatic and heretocyclic moiety containing 3 to 8 carbon atoms.

Specific examples of those compounds covered by the above generic formula are as follows: Compound No.

1 O-methyl-S-(p-ehlorophenyl)-methoxymethylphosphonodithioate 2 O-methyl-0 (1,Z-dicarbethoxy)ethyl-methoxymethylphosphonothionate 3 O-methyl-O-Z-pyrazinyl-methoxymethylphosphonothionate 4 O-methyl-S- (N-t.-butylcarbamoylmethyl) -methoxymethylphosphonodithioate 5 O-methyl-O- [4-(dimethyl-sulfamoyl)phenyl] -methoxymethylphosphonothionate 6 0-methyl-O-(4-cyanophenyl) -methoxymethylphosphonothionate 7 O-methyl-O-(4-nitrophenyl)-methoxymethylphosphonothionate 8 O-methyl-O-(2-chloro-4-nitro-phenyl)-n1ethoxymethylphosphonothionate 9 O-methyl-S-( 1,2-dicarbethoxy) ethyl-methoxymethylphosphonodithioate 10 O-ethyl-methoxymethylphosphonothionate O,O-diester with 4,4-thiodiphenol 11 O-ethyl-O-(4-nitrophenyl)-methoxyrnethylphosphonothionate l2 O-ethyl-O[4(dimethylsulfamoyl)-phenyl]-methoxymethylphosphonothionate 13 O-ethyl-S-[4-oxo-(1,2,3-benzotriazine-3 (4H )yl)- methyl]-methoxymethylphosphonodithioate 14 O-ethyl-S-(N-isopropylcarbamoylmethyl)-rnethoxymethylphosphonodithioate 15 O-ethyl-S- (N-methylcarbamoyloxymethyl) -methoxymethylphosphonodithioate 16 O-ethyl-O(2,3,5-trichloro-6-pyridyl)-methoxy methylphosphonothionate 17 O-ethyl-S- (4-nitrophenyl)-methoxymethylphosphonodithioate 18 O-ethyl-&(1,Z-dicarbomethoxy)ethyl-methoxymethylphosphonodithioate 19 0-ethyl-S- 1,2-dicarbethoxy) ethyl-methoxymethylphosphonodithioate 2O O,O'-diethyl-S,S'-n1ethylene-bis (methoxymethylphosphonodithioate) 21 ethyl-(4-nitrophenyl)-methoxymethylphosphonate 22 ethyl-[4(N,N-dimethylsulfamoyl) phenyl1-methoxymethylphosphonate 23 ethyl-(4-cyanophenyl)-methoxymethylphosphonate 24 ethyl-(1,2-dicarbethoxy) -ethyl-methoxymethylphosphonate 25 O-ethyl-S- 1,2-dicarbethoxy) ethyl-methoxyrnethylphosphonothionate 26 O-ethyl-O-(4-nitropheny1)-ethoxymethylphosphonothioate 27 O-ethyl-O-(4-cyanophenyl)ethoxymethylphosphonothionate 28 O-ethybO(3-methyl-4-methylthio)-phenyl-ethoxymethylphosphonothionate 29 ethyl- (4-nitrophenyl)-ethoxymethylphosphonate 30 ethyl-(4-cyanophenyl)-isopropoxymethylphosphonate 3 l ethyl- 1,2-dicarbethoxy)ethyl-isopropoxymethylphosphonate 32 O-ethyl-S[(6-chloro-2-oxo-3-benzoxazolinyl)methyl]-isopropoxymethylphosphonothionate 33 Oethyl-S(1,2-dicarbethoxy)ethyl-isopropoxymethylphosphonodithioate 34 O-ethyl-S-(methylthiomethyl)-isopropoxymethy1- phosphonodithioate 35 O-ethylS-(4-chlorophenylthio)methylisopropoxymethylphosphonodithioate 36 O,'O'-diethyl-S,S'-methylene-bis(isopropoxymethylphosphonodithioate) 37 O-ethy1-0- (2,3,S-trichloro-G-pyridyl) -isopropoxymethylphosphonothionate 38 O-ethyl-S-(4-cyanophenyl)-isopropoxymethylphosphonodithioate 39 O-ethyl-S-(4 chlorophenyl)-isopropoxymethylphosphonodithioate 40 O-ethyl-S-phenyl-isopropoxymethylphosphonodithioate 41 O-ethyl-S-(phthalimidomethyl)-isopropoxymethylphosphonodithioate 42 O-ethyl-S- ('6-chloro-2-oxo-3-benzoxazolinyl)methyl]-isopropoxymethylphosphonodithioate 43 O-ethyl-S- [4-oxo-1,2,3-benzotriazine-3 (4H)-yl methyl]-isopropoxymethylphosphonodithioate 44 O-ethyl-S- (2-methoxy-5-oxo-A -1,3,4-thiazolin-4- yl)methyl]methoxymethylphosphonodithioate 45 O-ethyl-S-(N-methylcarbamoylmethyl)-isopropoxymethylphosphonodithioate 46 O-ethyl-O- (4methylsulfonyl)-phenyl] -isopropoxymethylphosphonothionate 47 O-ethyl-O-[(N,N-dimethylsulfan1oyl)phenyl]-isopropoxymethylphosphonothionate 48 O-ethy1-O-(4-cyanophenyl)-isopropoxymethylphosphonothionate 49 O-ethyl-O- (4-N,N-dimethylcarbamoyl) -phenyl]- isopropoxymethylphosphonothionate O O-ethyl-O-(4-carbomethoxyphenyl)-isopropoxymethylphosphonothionate 5 1 O-ethyl-O-[ (3-trifiuoromethyl) -phenyl] -isopropoxymethylphosphonothionate 52 O-ethyl-O-(2,4,S-trichlorophenyl)-isopropoxymethylphosphonothionate 53 O-ethyl-O-(S-chlorophenyl)-isopropoxymethylphosphonothionate 54 0-ethyl-O[ (3-methyl-4-methylthio)-phenyl]-isopropoxymethylphosphonothionate 55 O-ethyl-O-(4-nitrophenyl)-isopropoxymethylphosphonothionate 56 O-ethyl-O-(3-methyl-4-nitrophenyl)-isopropoxymethylphosphonothionate 57 O-ethyl-S-(N-methylcarbamoyl)methyl-isopropoxymethylphosphonothiolate 58 O-ethyl-S-(N-isopropylcarbamoyl)methyl-isopropoxymethylphosphonodithioate 59 O-ethyI-S-(4-chlorophenylthiomethyl)-isopropoxymethylphosphonodithioate 60 O-ethyl-O-(4-nitrophenyl)-isobutoxymethylphosphonothionate 61 O-ethyl-O-[(4-N,N-dirnethylsulfamoyl)-phenyl]- isobutoxymethylphosphonothionate 62 Oethyl-O-(4cyanophenyl)-isobutoxymethylphosphonothionate 63 O-ethyl-O-(3-methyl-4-nitrophenyl)-methoxymethylphosphonothionate 64 O-ethyl-S-phenyl-methoxymethylphosphonodithioate 65 O-ethyl-O-(2,4,5-trichlorophenyl)-methoxymethylphosphonothionate 66 O-ethyl-O-[(3-methyl-4-methylthio)-phenyl]- methoxymethylphosphonothionate 67 O-ethyl-S-(4-chlorophenyl)-methoxymethylphosphonodithioate 68 O-ethyl-S-(4-nitrophenyl)-methoxymethylph0sphonothiolate 69 O-ethyl-S-(4-methylphenyl)-methoxymethy1phos phonodithioate 70 O-ethyl-O-(2,4dichlorophenyl)-methoxymethy1 phosphonothionate 71 O-ethyl-S-(phthalimidomethyl)-methoxymethylphosphonodithioate 72 O-ethyl-O- (4-chlorophenyl)-methoxymethylphosphonothionate 73 O-ethyl-O-(4-cyanophenyl)-methoxymethylphosphonothionate 74 O-ethyl-0-(4-methyl-2-oxo-2H-1-benzopyran-7- yl)-methoxymethylphosphonothionate 75 O-ethyl-S- (methylthiomethyl) -methoxymethylphosphonodithioate 76 0,0'-diethyl-S,S'-(oxydimethylene)-bis(methoxymethylphosphonodithioate) 77 O-ethyl-O-(2,4-dichlorophenoxymethy1)-methoxymethylphosphonothionate 4 78 0-(4-nitrophenyl)-S-ethyl-methoxymethylphosphonodithioate 79 O- (4-N,N-dimethylsulfamoyl)-phenyl]-S-ethylmethoxymethylphosphonodithioate 80 O-(4-cyanophenyl) -S-ethyl-methoxymethylphosphonodithioate.

The synthesis of these compounds can be represented by the following schematic equations:

This reaction is described in Kwiatek et al. US. 2,882,313 and in Chemical Abstracts 53, 16965 (1959).

Step 2:

This reaction is described in the following article: E. Uhing et al., JACS, 83, 2299 (1961).

This reaction is carried out according to the methods and examples described by F. W. Hoffman et a1. [(JACS, 80, 3945 (1958)] for phosphonate analogs of the subject intermediates. Therefore, the subject intermediates can be prepared according to these procedures described in this article and there is no need to go into any further detail at this time.

Another class of intermediates can be prepared according to the following schematic equation:

The preparation of these intermediates (O-alkylalkoxymethylphosphonodithioic acids) was carried out by using the method described by Szabo and Mann (JAFC, 17, 863 (1969).

A still further class of intermediates were prepared according to the following schematic equation:

between 5 and 20 C. The mixture of R SH and Base is gradually added to the 24 01, in inert solvent such as chloroform, methylene chloride, benzene toluene, ether, and the like.

A still further class of intermediates can be prepared according to the following schematic reactions.

This reaction is described in an article entitled: Z. Pelchovica, Jr., Journal of the Chemical Society, 1961, 238.

Any of these intermediates can then be reacted with either a mercaptan or an alcohol in the presence of a TABLE I.O -ALKYL-ALKOXYMETHYLPHO SPHONOTHIO LOTHION 1C ACID 8 Analysis Bollingpolnt P Calculated Found Millin.m.r., Yield, Compound Degrees meters my" ppm. H P S O H P S percent 0-ethyl-methoxymethylphosphonothiolothionie acid- 72-77 0.5 1.5333 92.9 25.8 6.9 16.6 34.5 26.0 5.9 16.5 34.4 77 0-methyl-methoxymethylphosphonothiolothionic ac 63-66 0.3 1.5489 96.2 21.0 6.3 18.0 37.3 20.0 5.4 18.3 36.9 0-ethyl-isopropoxymethylphosphonothiolothionlo 35 acid. 74-80 0.1 1.5127 -94.2 33.8 7.1 14.5 30.1 33.6 7.1 14.7 30.1 58

base The reaction is described for instance in the publi- E xample 2.Preparation of ethyl 1sopropoxymethylphosphonocation entitled: Houben-Weyl, Methoden der Organrehloridothionate schen Chemie, Parts 1 and 2, 1963; 1964. CH: s NaOEt CH s 0151'.

\ II II/ CHOOHrlCh CHOCHrP X 0B; X 0B; y B 1y i a z-- RZXH Z- Sodium ethoxlde (0.20 mole) 1n ethanol (100 ml.) was Cl KB:

This reaction is also described in the above-identified reference.

The following examples are set forth in order to further set out the novel features of the subject invention.

added dropwise during one hour and ten minutes to a stirred solution of isopropoxymethylphosphonothioic dichloride (39.9 g., 0.19 mole) in benzene (200 ml. at 2-4 in a nitrogen atmosphere. The reaction mixture was warmed to 26 during ten minutes, washed with water (3 X 250 ml.), and dried over anhydrous magnesium sulfate. The mixture was filtered, and the filtrate was rotary evaporated at /20 mm. to yield a colorless oil, 41 g. The oil was distilled through a 12" Vigreux to yield the product.

The gas chromatogram of the product (column, SE-30; temp. 110") had a peak at 3.6 min. (area, 95%) and peaks at 2.2 min. (area, 1%) and 5.0 min. (area, 4%). The infrared spectrum of the product had peaks 1100 cm.'- (C-O-C), and 1040 cmr 970 cm.

In like manner the following O-ethyl alkoxymethylphosphonochloridothioates were prepared:

TABLE II.O-ETHYL ALKOXYMETHYLPHOSPHONO CHLORIDOTHIOATES Analysis Boiling point P31 Calculated Found Percent Mflhn.m.r., purit Yield, Compound Degrees meters m3" p.p.m. G H 01 P S C H 01 P S by G. percent O-ethylmethoxymethylphosphono chlorodithioates ..100.5-103.5 16 1.4952 -92.9 25.5 5.4 18.8 16.4 17.0 25.7 5.4 18.8 16.3 17.3 93 79 0-ethylisopropoxymethylphosphono chlorodithioates. 61-63 0.1 1.4825 -93.4 33.4 6.5 16.4 14.3 14.8 33.6 6.5 16.3 14.3 14.9 95 61 O-ethyllsobutoxymethylphosphono chlorodlthioates. 54.5-57 0.13 1. 4781 -93.0 15.4 15.3 95 65 E l3.-P H 151 thlh 11 th' Example 1.---Preparatlo:1i11 1(1:102{1155!}igsaogsopoxymethylphosphonoxamp 9 on g figg gg yp asp Ono 010 CH; S 3KSH CE: E/OE'; O A S onoomi on -oomi c1. ms. -oen.i c1. C 3 C 3 SH Isopropoxymethylphosphonothioic dichloride (35.2 g., 0.17 mole) was added dropwise during thirty minutes to A stirred mixture of crude lS0pI0p0Xymcthy1ph 5 a stirred solution of sodium hydrosulfide (0.51 mole) in phonic dichloride (103.3 g., 0.54 m.),phosphorus pentaethanol (295 ml.) at --9 to -2 (Dry Ice-acetone coolsulfide (P 8 (26.3 g., 0.05 m.) and thiophosphoryl ing). The reaction mixture was evaporated at 50/20 chloride (186 ml.) was heated under nitrogen during five mm. for 20 minutes to yield a viscous opaque liquid. hours to by means of an oil bath. The mixture was Water ml.) was added to the liquid to yield a cloudy, heated at 110-115 for five hours. The reaction mixture yellow solution which was cooled to 10 by the addition was cooled to room temperature, and was diluted with of ice. Concentrated hydrochloric acid (20 ml.) was added 2x 300 ml. of n-hexane to yield an insoluble solid. The to the stirred solution at 0-10. The resulting mixture was 65 mixture was filtered and the solid was washed with hexextracted with methylene chloride (3X 200 ml.). The ane The filtrate was washed quickly with water (350 organic phase was dried with anhydrous magnesium sulml.), dried over anhydrous magnesium sulfate, filtered, fate, filtered, and the filtrate was evaporated at 40/ 20 and rotary evaporated at 50/20 mm. for two hours to mm. to yield a yellow liquid, 34.6 g. The liquid was fracyield a yellow liquid residue, g. The liquid was fractionated through a Vigreux column (8") to yield the 7 tionated with a 12" Vigreux column to yield the product. product. The infrared spectrum of the product had peaks The gas chromatogram of the product (column, 813-130; at 3100 cm. (aliphatic CH), 2550 cm. (S-H), temp. 85), had a peak at 3.8 min. (area, 98%) fol- 1090 cmr (C-O-C), and 1040 cmr' 960 cm.- lowed by a shoulder (area 2%) at 5.2 min. The infra- (P-O-C). red spectrum of the product had peaks at 2990 cm.-

The following 0 alkyl-alkoxymethylphosphonothiolo- 75 (aliphatic C-H) and 1090 cm.- (C-OC).

7 In like manner, the following alkoxymethylphosphonothioic dichlorides were prepared:

8 at 25/01 mm. to yield the product, a pale yellow oil,

6.1 g., 86% yield (n 1.5111). The oil had one major TABLE TIL-ALKOXYMETHYLPHOSPHONOTHIOIC DICHLO RIDES H Analysis Borhng point P Calculated Found Milhn.m.r., Yield, Compound Degrees meters m) p.p.m. C H D P S C H D P 8 percent;

Mathoxymethylphosphonothioic dichloride 83-85 1.5408 81.9 13.4 2.8 39.5 17.3 17.9 13.4 2.9 39.3 17.3 18.3 44 Ethoxymethylphosphonothioic dichloride 88.5-90 14 1.5261 80.4 16.6 17.3 35 Isopropoxymothylphosphonothioie dichloride 87.594.5 14 1.5146 83.0 23.2 4.4 34.2 15.0 15.5 23.4 4.5 34.0 15.0 15.7 40 Isobutoxymethylphosphonothioie dichloride 44.5-47 0.13 1.5084 81.5 27.2 5.0 32.2 14.5 27.4 4.9 33.0 15.0 33

Example 4.-Preparation of ethyl-methoxymethylphosphono- 15 k (96% b i th gas chromatogram t 72 chloridothlonate with N,N-dlmethyl-phydroxy-beuzenesulfouamide Ethyl-methoxymethylphosphonochloridothionate (2.84 g., 15 mmoles) was added all at once to a solution of N,N-dimethyl-phydroxybenzenesulfonamide (3.01 g., 15 mmoles) and triethylamine (1.71 g., 17 mmoles) in acetone (30 ml.). A white solid started to separate after a few minutes. The reaction mixture was heated under reflux for 2 hours and 15 minutes. The mixture was cooled, and filtered to yield a white solid, triethylamine hydrochloride (1.73 g., 84% yield). The filtrate was evaporated at 40/20 mm. to yield an amber oil. A benzene solution of the oil (50 ml.) was washed with water (50 m1.) and was dried over magnesium sulfate. The mixture was filtered and evaporated at 50/20 mm. and at 25 0.1 mm. to yield the product, a yellow oil, 4.8 g., 91% yield 1.5363).

Analysis. Calcd for C H NO PS (percent): C=40.9; H=5.8; N=4.0. Found (percent): C=41.0; H=6.1; N=4.1. The infrared spectrum of the product had peaks of 1340 cm.- and 1150 cm.- (SO and at 1100 cmf and 1020 cm.- (P-OC). The product had one peak in the P n.m.r. spectrum at -86.5 p.p.m. (H PO Example 5.Preparation of ethyl-methoxymethylphosphonochloridothionate with dimethyl-mereaptosuccinate SRz CHsOCHn S \ll P-Cl SH-CH-COOCHa om-oooom CHsOCH: S

P'S(IJHCOOCH8 EtO CHz-COOCH:

A solution of triethylamine (2.35 g., 23 mmoles) and dimethyl-mercaptosuccinate (3.78 g., 21 mmoles) in ben- EtO zene ml.) was added dropwise to a stirred solution of min. (T=1-85, 5% SE-30 on Chrom. W., 5 ft. column, N =16 p.s.i.).

Analysis.Calcd. tor C H O PS (percent): C: 36.4; H=5.8; P=9.4; S=19.4. Found (percent): C=36.4; H='6.0; P=9.7; S=19.7. The infrared spectrum of the product had a peak at 1740 cm.- (0:0) and peaks at 1100 cm.- and 1020 cm.- (POC). The product had one peak in the P n.m.r. spectrum at 98.3 p.p.m. H PO Example 6.Preparation of ethyl methoxymethylphosphonochloride with p-cyanophenol 2 OR] z-l ORz CHaOCHz O l er HO@CN EtO CHsOCH: O

1 0 m EtO A solution of ethyl-methoxymethylphosphonochloridate (3.45 g., 20 mmoles) in acetone (10 ml.) was added all at once to a solution of triethylamine (2.12 g., 21 moles and p-cyanophenol (2.38 g., 20 mmoles) in acetone (20 ml.). There was an exothermic reaction and a white solid separated. The mixture was heated under reflux for one-half hour and then allowed to stand overnight at room temperature. The mixture was filtered to yield a solid, triethylamine hydrochloride, 2.44 g., 89% yield. The filtrate was added to water ml.). Salt was added to the resulting mixture and the mixture extracted with dichloromethane (100 ml.; 50 ml.). The organic phase was washed with 5% sodium carbonate solution (100 ml.) and water (3X 100 ml.) The organic phase was dried (MgSO filtered and evaporated at 50/20 mm. and then 50/0.1 mm. to yield the product a pale yellow liquid, 4.6 g., 90% yield, 11 1.5086. The product had one peak in the gas chromatogram at 2.8 min. (T=, 5% SE-30 on Chromosorb W., '5 ft. column, N =16 p.s.i.).

The infrared spectrum of the product had a peak at 2280 cm.- (CN) and peaks at 1120 cm.- and 1040 cm.- (P--OC).

Example 7.-Preparatl0n of ethyl methoxymethylphosphonochloride with dlethylmercaptosuccinate 2 OR; z-l

CHaOCH: 0 HS CH 000E \{LCI H 000E: mo

CHgOCH: 0

P-S-CH-COO Et EtO Hz-GOOEt Ethyl-rnethoxymethylphosphonochloridate (3.45 g., 20 mmoles) in acetone ml.) was added all at once to a solution of triethylamine (212 g., 21 mmoles) and diethylmercaptosuccinate (4.12'g., 2O mmoles) in acetone ml.) immersed in a water bath. There was an immediate precipitate and an exothermic reaction. The mixture was heated under reflux for 20 minutes and then allowed to cool to room temperature. The mixture was filtered to yield a white solid, triethylamine hydrochloride, 2.56 g., 93% yield. The filtrate was poured into the product, a yellow liquid, 5.4 g., 80% yield, n 1.4716. On standing, the product became cloudy with a small amount of solid. The cloudy oil was filtered to yield a clear yellow liquid. The gas chromatogram o f the liquid had one peak at 5.7 min. (T=185, 5% SE- on Chrom. W., 5 ft. column, N ='16 p.s.i.). The infrared spectrum of the liquid had a peak at 1740 cm.- (C=O) and peaks at 1120 cm. and 1040 cm." (P OC). The P n.m.r. had a major peak 90%) at 45.9 p.p.rn. (H PO water (100 ml.). This mixture was extracted with di- 0 Other compounds of this invention were prepared by chloromethane. The organic phase was washed with 5% methods given in Examples 4 to 7. The structure of sodium carbonate solution (100 m1.), and water (200 these compounds were confirmed by infrared and NMR ml.). The organic phase was dried (MgSO filtered, spectroscopy. They were also characterized by refractive and evaporated at /20 mm. and 0.1 mm. to yield indices which are listed in the following table:

TABLE IV 52" zoom-P Compound No. Z R; R; X Y 92 20 1 Me Me s 3 1.6170

2..:; Me Me -OHO0Et s 0 1.4960

OH COOEt 3...: Me Me IN S 0 1.5357

4 Me Me I S S 1.5337

oHioNH-t-Bu 5 Me Me S 0 1. 5455 --SO2NMe2 6 Me Me s 0 1.5515

7 Me Me s 0 1.5621

8 Me Me S 0 1.5697

9 Me Me t S 8 1.5073

CHzCOOEt 1o- Me Et: s s 0 1. 5751 11 Me Er s 0 1.5537

12 Me Ea s 0 1.5383

- SOzNMe:

1a Me E1; s s 1. 6176 'OHg-ITI N 14 Me Et C 2fiNHiPr s s 1. 5373 15 Me E5 CHzCII |IHMe s s 1. 5492 16 Me E1; s 0 1.5555

TABLE IV-Continued Compound No. Z R R; m)

17 M9 ET B 1. (W54 18 M Et CH-CO OCH; 8 1.5009

CHzC O O CH! 19 Me Et CH--CO 0E1; S 1. 4978 20 a M6 Et 8 1. 5485 lCH L SOzNMez 24 Me Et CH-COOEI; 0 1.4402

OHz-C O 0 E1;

25 Me Et CHC O 0131; S 1. 4720 C H2-C O 0 Et 27 Et t 0 1. 5325 28 Et t CH: O 1. 5465 6 29 E15 E13 0 1. 5173 30 i-PI E17 0 1. 5007 31 i-Pr Et CH-GOOEt O 1. 4411 CHaC O 0 Et 32...;-..:.." i-Pr El; 0 1. 5364 CH2-N 33....'-::: i-Pr Et CH-COOEt S 1. 4945 C Hz-C O 0 Et 34...:;:::::.:. 1-1! E17 CHz- S CH3 8 1. 5317 35 .J. i-PI E13 S 1. 5858 CH2 S Cl 36 .2: i-Pr Et S 1. 5405 -CHz 37....1::. i-Pr E1; 0 1. 5401 C1- 0 C1 C1 N 38...:;:-:..' i-Pt Et S 1. 5729 39 i-Pr Et 5 1. 5677 40 i-Pt Et 1 S 1. 5568 The compounds of the invention have general insecticidal properties. Insecticidal compositions of the invention are prepared by admixing one or more of the active ingredients defined heretofore, in insecticidally effective amounts with a conditioning agent of the kind used and referred to in the art as 'a pest control adjuvant or modi- -fier to provide formulations adapted for ready and eflicient application to the soil using conventional applicator equipment.

Thus, the insecticidal compositions or formulations are prepared in the form of solids or liquids. Solid compositions are preferably in the form of granulars or dusts.

The compositions can be compounded to give homogeneous free-flowing dusts by admixing the active compound or compounds with finely divided solids preferably talc, natural clays, pyrophyllite, diatomaceous earth, or flours such as walnut shell, wheat, redwood, soya bean, and cottonseed flours. Other inert solid conditioning agents or carriers of the kind conventionally employed in preparing pest control compositions in powdered from can be used.

Granulars can be compounded by absorbing the compound in liquid form onto a preformed granular diluent. Such diluents as natural clays, pyrophyllite, diatomaceous earth, flours such as walnut shell, as well as granular sand can be employed.

In addition, granulars can also be compounded by admixing the active ingredient with one of the powdered diluents described hereinabove, followed by the step of either pelleting or extruding the mixture.

Liquid compositions of the invention are prepared in the usual Way by admixing one or more of the active ingredients with a suitable liquid diluent medium. 'In the cases where the compounds are liquids, they may be sprayed in ultra low volume as such. With certain solvents, such as alkylated naphthalene or other aromatic petroleum solvents, dimethyl formamide, cycloketone, relatively high up to about 50% by weight or more concentration of the active ingredient can be obtained in solution.

The insecticidal compositions of the invention whether in the form of dusts or liquids, preferably also include a surface-active agent sometimes referred to in the art as a wetting, dispersing, or emulsifying agent. These agents, which will be referred to hereinafter more simply as surface-active dispersing agents, cause the compositions to be easily dispersed in Water to give aqueous sprays which, for the most part, constitute a desirable composition for application.

The surface-active dispersing agents employed can be of the anionic, cationic, or nonionic type and include, for example, sodium and potassium oleate, the amine salts of oleic acid, such as morpholine and dimethylamine oleates, the sulfonated animal and vegetable oils, such as sulfonated fish and castor oils, sulfonated petroleum oils, sulfonated acyclic hydrocarbons, sodium salt of lignin sulfonic acid (goulac), alkylnaphthalene sodium sulfonate, sodium salts of sulfonated condensation products of naphthalene and formaldehyde, sodium lauryl sulfate, disodium monolauryl phosphate, sorbitol laurate, pentaerythritol monostearate, glycerol monostearate, diglycol oleate, polyethylene oxides, ethylene oxide condensation products with stearyl alcohol and alkylphenol, polyvinyl alcohols, salts, such as the acetate of polyamines from reductive amination of ethylene/carbon monoxide polymers, laurylamine hydrochloride, lauryl-pyridiniurn bromide, stearyl trimethylammonium bromide, cetyl-dimethylbenzyl ammonium chloride, lauryldimethylamine oxide, and the like. Generally, the surface-active agent will not compirse more than about to 15% by weight of the composition, and in certain compositions the percentage will be 1% or less. Usually, the minimum lower concentration will be 0.1%.

The insecticidal compositions are applied either as a spray, granular or a dust to the locus or area to be protected from undesirable insects. Such application can be made directly upon the locus or area and the insects thereon during the period of infestation in order to destroy the insects, but preferably, the application is made in ad vance of an anticipated insect infestation to prevent such infestation. Thus, the compositions can be applied as aqueous foliar sprays but can also be applied as sprays directly to the surface of the soil. Alternatively, the dry powdered compositions can be dusted directly on the plants or on the soil.

The active compound is, of course, applied in an amount suflicient to exert the desired insecticidal action. The amount of the active compound present in the compositions as actually applied for destroying or preventing infestation by the insects will vary with the manner of application, the particular insect for which control is sought, the purpose for which the application is being made, and like variables. In general, the insecticidal compositions as applied in the form of a spray, dust or granular, will contain from about 0.1% to 100% by weight of the active compound.

The term carrier or diluent as used herein means a material, which can be inorganic or organic and synthetic or of natural origin, with which the active ingredient is mixed or formulated to facilitate its storage, transport, and handling and application to the plants to be treated. The carrier is preferably biologically and chemically inert and, as used, can be a solid or fluid. When solid carriers are used, they are preferably particulate, granular, or pelleted; however, other shapes and sizes of solid carrier can be employed as well. Such preferable solid carriers can be natural occurring mineralsalthough subsequently subjected to grinding, sieving, purification, and/or other treatments-including, for example, gypsum; tripolite; diatomaceous earth, mineral silicates such as mica, vermiculite, talc, and pyrophyllite; clays of the montmorillonite, kaolinite, or attapulgite groups; calcium or magnesium limes, or calcite and dolomite; etc. Carriers produced synthetically, as for example, synthetic hydrated silica oxides and synthetic calcium silicates can also be used, and many proprietary products of this type are available commercially. The carrier can also-be an elemental substance such as sulfur or carbon, preferably an activated carbon. If the carrier possesses intrinsic catalytic activity such that it would decompose the active ingredient, it is advantageous to incorporate a stabilizing agent, as for example, polyglycols such as diethylene glycol, to neutralize this activity and thereby prevent possible decomposition of the present compounds.

For some purposes, a resinous or waxy carrier can be used, preefrably one which is solvent soluble or thermoplastic, including fusible. Examples of such carriers are natural or synthetic resins such as a coumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride, styrene polymers and copolymers, a solid grade of polychlorophenol such as is available under the registered trademark Aroclor, a bitumen, an asphaltite, a wax for example, beeswax or a mineral wax such as paraffin wax or montan wax, or a chlorinated mineral wax, or a microcrystalline wax such as those available under the registered trademark Mikrovan Wax. Compositions comprising such resinous or waxy carriers are preferably in granular or pelleted form.

Fluid carriers can be liquids, as for example, water, or an organic fluid, including a liquefied normally vaporous or gaseous material, or a vaporous or gaseous material, and can be solvents or nonsolvents for the active material. For example, the horticultural petroleum spray oils boiling in the range of from about 275 to about 575 F., or boiling in the range of about 575 to about 1,000" P. and having an unsulfonatable residue of at least about 75% and preferably of at least about or mixtures of these two types of oil, are particularly suitable liquid carriers.

The carrier can be mixed or formulated with the active material during its manufacture or at any stage subsequently. The carrier can be mixed or formulated with the active material in any proportion depending on the nature of the carrier. One or more carriers, moreover, can be used in combination.

The compositions of this invention can be concentates, suitable for storage or transport and containing, for example, from about to about 90% by weight of the active ingredient, preferably from about 20 to about 80 wt. percent. These concentrates can be diluted with the same or different carrier to a concentration suitable for application. The compositions of this invention may also be dilute compositions suitable for application. In general, concentrations of about 0.1 to about 10% by weight, of active material based on the total weight of the compositions are satisfactory, although lower and higher concentrations can be applied if necessary.

The compositions of this invention can also be formulated as dusts. These comprise an intimate admixture of the active ingredient and a finely powdered solid carrier such as aforedescribed. The powdered carriers can be oil treated to improve adhesion to the surface to which they are applied. These dusts can be concentrates, in which case a highly sorptive carrier is preferably used. These require dilution with the same or a different finely powdered carrier, which can be of lower sorptive capacity, to a concentration suitable for application.

The compositions of the invention can be formulated as wettable powders comprising a major proportion of the active ingredient mixed with a dispersing, i.e., defiocculating or suspending agent, and if desired, a finely divided solid carrier and/or a wetting agent. The active ingredient can be in particulate form or adsorbed on the carrier and preferably constitutes at least about 10%, more preferably at least about by weight of the composition. The concentration of the dispersing agent should in general be between about 0.5 and about 5% by weight of the total composition, although larger or smaller amounts can be used if desired.

The dispersing agent used in the composition of this invention can be any substance having definite dispersing, i.e., defiocculating or suspending, properties as distinct from wetting properties, although these substances can also possess wetting properties as well.

The dispersant or dispersing agent used can be protective colloids such as gelatin, glue, casein, gums, or a synthetic polymeric material such as polyvinyl alcohol and methyl cellulose. Preferably, however, the dispersants or dispersing agents used are sodium or calcium salts of high molecular weight sulfonic acids, as for example, the sodium or calcium salts or lignin sulfonic acids derived from sulfite cellulose waste liquors. The calcium or sodium salts of condensed aryl sulfonic acid, for example, the products known as Tamol 731, are also suitable.

The wetting agents used can be nonionic type surfactants, as for example, the condensation products of fatty acids containing at least 12, preferably 16 to 20, carbon atoms in the molecule, or abietic acid or naphthenic acid obtained in the refining of petroleum lubricating oil fractions with alkylene oxides such as ethylene oxide or propylene oxide, or with both ethylene oxide and propylene oxide, as for example, the condensation product of oleic acid and ethylene oxide containing about 6 to 15 ethylene oxide units in the molecule. Other nonionic wetting agents like polyalkylene oxide polymers, commercially known as Pluronics can be used. Partial esters of the above acids with polyhydric alcohols such as glycerol, polyglycerol, sorbitol, or mannitol can also be used.

Suitable anionic wetting agents include the alkali metal salts, preferably sodium salts, of sulfuric acid esters or sulfonic acids containing at least 10 carbon atoms in a molecule, for example, the sodium secondary alkyl sul- 20 fates, dialkyl sodium sulfosuccinate available under the registered trademark Teepol, sodium salts of sulfonated castor oil, sodium dodecyl benzene sulfonate.

Granulated or pelleted compositions comprising a suitable carrier having the active ingredient incorporated therein are also included in this invention. These can be prepared by impregnating a granular carrier with a solution of the inert ingredient or by granulating a mixture of a finely divided solid carrier and the active ingredient. The carrier used can consist of or contain a fertilizer or fertilizer mixture, as for example, a superphosphate.

The compositions of this invention can also be formulated as solutions of the active ingredient in an organic solvent or mixture of solvents, such as for example, alcohols; ketones, especially acetone; ethers, hydrocarbons, etc.

Where the toxicant itself is a liquid these materials can be sprayed on crops or insects without further dilution.

Petroleum hydrocarbon fractions used as solvents should preferably have a flash point above 73 R, an example of this being a refined aromatic extract of kerosene. Auxiliary solvents such as alcohols, ketones, and polyalkylene glycol ethers and esters can be used in conjunction with these petroleum solvents.

Compositions of the present invention can also be formulated as emulsifiable concentrates which are concentrated solutions or dispersion of the active ingredient in an organic liquid, preferably a water-insoluble organic liquid, containing an added emulsifying agent. These concentrates can also contain a proportion of water, for example, up to about by volume, based on the total composition, to facilitate subsequent dilution with water. Suitable organic liquids include, e.g., the above petroleum hydrocarbon fractions previously described. Higher concentrations may be prepared using polar cosolvents such as cyclohexanone or dimethylformamide.

The emulsifying agent can be of the type producing water-in-oil type emulsions which are suitable for application by low volume spraying or an emulsifier of the type producing oil-in-water emulsions can be used, producing concentrates which can be diluted with relatively large volumes of water for application by high volume spraying or relatively small volumes of water for low volume spraying. In such emulsions, the active ingredient is preferably in a nonaqueous phase.

The present invention is further illustrated in greater detail by the following examples, but it is to be understood that the present invention in its broadest aspects is not necessarily limited in terms of the reactants or specific temperatures, residence times, separation techniques and other process conditions, etc.; or dosage level, exposure times, test species used, etc. by which the compounds and/or compositions described and claimed are prepared and/or used.

In the examples which follow, the compounds were treated in the greenhouse and in the laboratory to determine their biological activity.

The experimental compounds were tested as aqueous emulsions. These emulsions were prepared by dissolving the compound in acetone and dispersing it in distilled water with Triton Xl00, an alkalaryl polyether alcohol derived by the reaction of i-octyl phenol with ethylene oxide, to give spray emulsions containing the desired concentration of the compound. These emulsions were then used in standard laboratory tests described below.

Mexican bean beetle: Bean leaves were dipped in the emulsion of the test chemical and allowed to dry. The individual treated leaves were placed in Petri dishes and five Mexican bean beetle larvae introduced into each of the two replicate dishes.

Mites, contact: Potted bean plants infested with the two-spotted spider mites were placed on a turntable and sprayed with a formulation of the test chemical. The

plants were held for seven days and the degree of mite control was rated after this period.

Mites, systemic: Bean plants were treated by applying ml. of the formulated test chemical to the soil. The mites were transferred to the plants after 24 hours. The plants were held for seven more days and the degree of mite control rated.

Aphid, contact: Potted nasturtium plants infested with the bean aphids were placed on a turntable and sprayed with a formulation of the test chemical. The plants were held for two days and the degree of aphid control was rated.

Aphid, systemic: Nasturtium plants were treated by applying 20 ml. of the formulated test chemical to the soil. The mites were transferred to the plants after 24 hours. The plants were held for 48 additional hours and the degree of the Aphid control rated.

Southern army worm: Bean leaves were dipped in the emulsion of the test chemical of desired concentration and allowed to dry. The individual treated leaves were placed in Petri dishes and five southern army larvae introduced into each of the two replicate dishes. The plants were held for two days and the degree of control was rated.

Some of the compounds were also tested against other species of coleoptera family such as confused flour beetle and spider beetle, as well as adult Mexican bean beetles. They were also tested for their effectiveness to control German cockroaches and houseflies. Tests were also done to determine their ovicidal action. The compounds were found active in one or more of these tests.

Representative data for a number of compounds demonstrating their insecticidal activity are presented in Table V.

TABLE V Mites Aphids Con- Sys- Con- Sys- MBB tact temie tact temic SAW HF TABLE V-C0ntinued Mites Aphids Con- Sys Con- Sys- Number MBB tact temic tact temic SAW HF What is claimed is: 1. Compounds of the formula:

wherein Z is a C to C alkyl-OCH group; X is either 0 or S; R is a C to C alkyl group; R is phenyl substituted by chloro, nitro or lower alkyl.

2. A compound of claim 1 wherein R is chloro substituted phenyl.

3. A compound according to claim 1, O-methyl-S-(pchlorophenyl)-methoxymethylphosphonodithioate.

4. A compound according to claim 1, O-rnethyl-O-(4- nitrophenyl)-methoxymethylphosphonothionate.

5. A compound according to claim 1, O-methyl-O-(Z- chloro 4 nitro-phenyl)-methoxymethylphosphonothionate.

References Cited UNITED STATES PATENTS 3,078,212 2/ 1963 Newallis et al. 260940 X 3,153,663 10/1964 Sirrenberg et al. 260949 X 3,351,682 11/1967 Baker et al 260949' X 3,600,470 8/1971 Lewis 260-950 X LEWIS GOTTS, Primary Examiner R. L. RAYMOND, Assistant Examiner U.S. Cl. X.R.

260-248 R, 251 P, 290 R, 307 D, 326 R, 928, 929, 940, 941, 942, 943, 944, 945, 948, 94-9, 951, 972, 973, 979; 424-200, 205, 206, 210, 211, 212, 216, 217 

